Radiation-sensitive composition and method of fabricating a device using the radiation-sensitive composition

Abstract

A radiation-sensitive composition (and method of fabricating a device using the composition) includes a nonpolymeric silsesquioxane including at least one acid labile moiety, a polymer including at least one member selected from the group consisting of an aqueous base soluble moiety and an acid labile moiety, and a radiation-sensitive acid generator. Another radiation-senstive composition (and method of fabricating a device using the composition) includes a nonpolymerc silsesquioxane including at least one aqueous base soluble moiety, a polymer including an aqueous base soluble moiety, a crosslinker, and a radiation-sensitive acid generator.

1. A radiation-sensitive composition, comprising:
 a nonpolymeric silsesquioxane comprising at least one acid labile moiety; 
 a polymer comprising at least one member selected from a group consisting of an aqueous base soluble moiety and an acid labile moiety; and 
 a radiation-sensitive acid generator, 
 wherein said polymer is selected from a group consisting of polyacrylates, polymethacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and a mixture thereof, and 
 wherein said nonpolymeric silsesquioxane is present in a range from more than 10 wt % to 94 wt % of solids in said composition. 
 
     
     
       2. The radiation-sensitive composition of  claim 1 , wherein said nonpolymeric silsesquioxane is selected from a group consisting of:
 a polyhedral silsesquioxane optionally having one to three open vertices; and 
 a macromer of two to four polyhedral silsesquioxanes that may be the same or different, with each polyhedral silsesquioxane optionally having one to three open vertices. 
 
     
     
       3. The radiation-sensitive composition of  claim 2 , wherein said polyhedral silsesquioxane comprises from 4 to 10 faces. 
     
     
       4. The radiation-sensitive composition of  claim 1 , wherein said acid labile moiety in said nonpolymeric silsesquioxane and said acid labile moiety in said polymer are selected from a group consisting of ethers, acetals, ketals, ortho esters, carboxylic esters, carbonates, and sulfonates. 
     
     
       5. The radiation-sensitive composition of  claim 1 , wherein said aqueous base soluble moiety is selected from a group consisting of a hydroxyl, a fluoroalcohol, a carboxylic acid, an amino group, and an imino group. 
     
     
       6. The radiation-sensitive composition of  claim 1 , wherein said radiation-sensitive acid generator is selected from a group consisting of nitrobenzyl compounds, sulfonium salts, iodonium salts, sulfonates, and carboxlates. 
     
     
       7. An imaging layer for patterning a substrate, said imaging layer comprising the radiation-sensitive composition of  claim 1 . 
     
     
       8. A bilayer resist layer for patterning a substrate, comprising:
 an underlayer formed on said substrate; and 
 the imaging layer of  claim 7  formed on said underlayer. 
 
     
     
       9. The radiation-sensitive composition of  claim 1 , wherein said acid labile moiety in said nonpolymeric silsesquioxane is covalently bound to a silicon atom in said nonpolymeric silsesquioxane. 
     
     
       10. The radiation-sensitive composition of  claim 1 , wherein said acid labile moiety in said nonpolymeric silsesquioxane comprises a structure of formula (I):
   -(L 1 ) m -(X) n -[(L 2 ) q -R 1 ] r   (I)
 
 wherein m, n, and q are independently zero or 1, r is an integer of at least 1 indicating the number of (L 2 ) q -R 1  present, and L 1 , X, L 2 , and R 1  are as follows:
 L 1  comprises a member selected from a group consisting of —O—SiR 2 R 3 —, C 1 -C 12  alkylene, substituted C 1 -C 12  alkylene (e.g., C 1 -C 12  fluoroalkylene or hydroxyl-substituted C 1 -C 12  alkylene), C 1 -C 12  heteroalkylene (e.g., C 1 -C 6  alkoxy-substituted C 1 -C 6  alkylene), substituted C 1 -C 12  heteroalkylene (e.g., C 1 -C 6  alkoxy- or hydroxyl-substituted C 1 -C 6  fluoroalkylene), C 5 -C 14  arylene, substituted C 5 -C 14  arylene (e.g., C 5 -C 14  fluoroarylene or hydroxyl-substituted C 5 -C 14  arylene), C 5 -C 14  heteroarylene (e.g., pyridinyl, pyrimidinyl, furanyl), substituted C 5 -C 14  heteroarylene, C 6 -C 14  aralkylene, substituted C 6 -C 14  aralkylene, C 6 -C 14  heteroaralkylene, and substituted C 6 -C 14  heteroaralkylene, wherein R 2  and R 3  are hydrogen or C 1 -C 12  hydrocarbyl, wherein when L 1  is optionally substituted and/or heteroatom-containing C 3 -C 12  alkylene, L 1  is linear, branched, or cyclic; 
 X comprises a member selected from a group consisting of C 3 -C 30  alicyclic and substituted C 3 -C 30  alicyclic; and 
 L 2  comprises a member selected from a group consisting of C 1 -C 12  alkylene, substituted C 1 -C 12  alkylene, C 1 -C 12  heteroalkylene, substituted C 1 -C 12  heteroalkylene, C 5 -C 14  arylene, substituted C 5 -C 14  arylene, C 5 -C 14  heteroarylene, substituted C 5 -C 14  heteroarylene, C 6 -C 14  aralkylene, substituted C 6 -C 14  aralkylene, C 6 -C 14  heteroaralkylene, and substituted C 6 -C 14  heteroaralkylene, wherein when L 2  is optionally substituted and/or heteroatom-containing C 3 -C 12  alkylene, L 2  is linear, branched, or cyclic; and R 1  is selected from acid-cleavable ester, oligomeric ester, ether, carbonate, acetal, ketal, and orthoester substituents. 
 
 
     
     
       11. The radiation-sensitive composition of  claim 1 , wherein said polymer is selected from a group consisting of polyacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and a mixture thereof. 
     
     
       12. The radiation-sensitive composition of  claim 1 , wherein said polymer comprises a non silsesquioxane polymer. 
     
     
       13. A method of fabricating a device, said method comprising:
 applying a radiation-sensitive composition to a substrate to form a resist layer on said substrate, said composition comprising:
 a nonpolymeric silsesquioxane comprising at least one acid labile moiety, 
 a polymer comprising at least one member selected from a group consisting of an aqueous base soluble moiety and an acid labile moiety; and 
 a radiation-sensitive acid generator; 
 
 patternwise exposing said resist layer to radiation, to generate acid in exposed regions of said resist layer; 
 removing patternwise soluble portions of said resist layer to form a pattern of spaces in said resist layer; and 
 transferring said pattern of spaces to said substrate, 
 wherein said polymer is selected from a group consisting of polyacrylates, polymethacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and a mixture thereof, and 
 wherein said nonpolymeric silsesquioxane is present in a range from more than 10 wt % to 94 wt % of solids in said composition. 
 
     
     
       14. The method of  claim 13 , further comprising:
 baking the exposed resist layer to promote acid-catalyzed reaction in exposed portions of said resist layer subsequent to said patternwise exposing said substrate. 
 
     
     
       15. The method of  claim 13 , further comprising:
 forming a planarizing layer over said substrate, said resist layer being applied directly to said planarizing layer. 
 
     
     
       16. The method of  claim 13 , wherein said transferring said pattern comprises performing an anisotropic etch to transfer said pattern. 
     
     
       17. The method of  claim 13 , wherein said patternwise exposing said resist layer to said radiation generates said acid such that said acid labile moiety in said nonpolymeric silsesquioxane is cleaved from said nonpolymeric silsesquioxane. 
     
     
       18. A radiation-sensitive composition, comprising:
 a nonpolymeric silsesquioxane comprising at least one aqueous base soluble moiety; 
 a polymer comprising an aqueous base soluble moiety; 
 a crosslinker; and 
 a radiation-sensitive acid generator, 
 wherein said polymer is selected from a group consisting of polyacrylates, polymethacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and a mixture thereof, and 
 wherein said nonpolymeric silsesquioxane is present in a range from more than 10 wt % to 94 wt % of solids in said composition. 
 
     
     
       19. The radiation-sensitive composition of  claim 18 , wherein said nonpolymeric silsesquioxane is selected from a group consisting of:
 a polyhedral silsesquioxane optionally having one to three open vertices; and 
 a macromer of two to four polyhedral silsesquioxanes that may be the same or different, with each polyhedral silsesquioxane optionally having one to three open vertices. 
 
     
     
       20. The radiation-sensitive composition of  claim 19 , wherein said polyhedral silsesquioxane comprises from 4 to 10 faces. 
     
     
       21. The radiation-sensitive composition of  claim 18 , wherein said aqueous base soluble moiety is selected from a group consisting of a hydroxyl, a fluoroalcohol, a carboxylic acid, an amino group, and an imino group. 
     
     
       22. The radiation-sensitive composition of  claim 18 , wherein said radiation-sensitive acid generator is selected from a group consisting of nitrobenzyl compounds, sulfonium salts, iodonium salts, sulfonates and carboxlates. 
     
     
       23. A method of fabricating a device, said method comprising:
 applying a radiation-sensitive composition to a substrate to form a resist layer on said substrate, said radiation-sensitive composition comprising:
 a nonpolymeric silsesquioxane comprising at least one aqueous base soluble moiety; 
 a polymer comprising an aqueous base soluble moiety; 
 a crosslinker; and 
 a radiation-sensitive acid generator; 
 
 patternwise exposing said resist layer to radiation, to generate acid in exposed regions of said resist layer; 
 removing patternwise soluble portions of said resist layer to form a pattern of spaces in said resist layer; and 
 transferring said pattern of spaces to said substrate, 
 wherein said polymer is selected from a group consisting of polyacrylates, polymethacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and a mixture thereof, and 
 wherein said nonpolymeric silsesquioxane is present in a range from more than 10 wt % to 94 wt % of solids in said composition. 
 
     
     
       24. The method of  claim 23 , further comprising:
 baking the exposed resist layer to promote acid-catalyzed reaction in exposed portions of said resist layer subsequent to said patternwise exposing of said substrate. 
 
     
     
       25. The method of  claim 23 , further comprising:
 forming a planarizing layer over said substrate, said resist layer being applied directly to said planarizing layer. 
 
     
     
       26. The method of  claim 23 , wherein said transferring said pattern comprises performing an anisotropic etch to transfer said pattern. 
     
     
       27. A radiation-sensitive composition, comprising:
 a nonpolymeric silsesquioxane comprising at least one acid labile moiety; 
 a polymer comprising at least one member selected from a group consisting of an aqueous base soluble moiety and an acid labile moiety; and 
 a radiation-sensitive acid generator, 
 wherein said nonpolymeric silsesquioxane is present in a range from more than 10 wt % to 94 wt. % of solids in said composition, and 
 wherein said polymer is selected from a group consisting of polyacrylates, polymethacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and thereof. 
 
     
     
       28. A radiation-sensitive composition, comprising:
 a nonpolymeric silsesquioxane comprising at least one acid labile moiety; 
 a polymer comprising at least one member selected from a group consisting of an aqueous base soluble moiety and an acid labile moiety; and 
 a radiation-sensitive acid generator, 
 wherein said polymer is present in a range from 5 wt % to 91 wt % of solids contained in said composition, and 
 wherein said polymer is selected from a group consisting of polyacrylates, polymethacrylates, polycyclicolefins, cyclicolefine-maleic anhydride copolymers, and a mixture thereof, and 
 wherein said nonpolymeric silsesquioxane is present in a range from more than 10 wt % to 94 wt % of solids in said composition.